Graphene polymer conductive film and method of manufacturing the same

Abstract

The present invention provides a graphene polymer conductive film and a method of manufacturing the graphene polymer conductive film. The method uses a graphene conductive polymer as conductive filler such that the drawbacks of the conventional conductive film such as exceeded filler content, expensive, complex manufacturing process and high environment pollution. The manufacture of graphene uses the method of in situ polymerization such that the conductive polymer and the graphene are distributed more uniformly, the produced graphene conductive polymer is with good stability, and the conductivity is proved. The present invention further realizes size control of the graphene conductive polymer in the process of manufacturing the graphene conductive polymer through adjusting the ratio of raw materials of the graphene and the conductive monomers. The graphene polymer conductive film produced by the present invention has advantages of high conductivity, environment friendly, etc., and could be applied in a thin film transistor liquid crystal display for substituting conductive golden film or conductive silver film, or applied in connecting superfine circuitry.

What is claimed is: 
     
         1 . A method of manufacturing a graphene polymer conductive film, comprising:
 step  1  for providing a powder of a graphene and a plurality of conductive monomers;   step  2  for providing a solvent and producing a graphene dispersion liquid by stirring and ultrasonic processing the solvent after mixing the powder of the graphene into the solvent;   step  3  for producing a mixed liquid having the graphene and the conductive monomers uniformly distributed by stirring and ultrasonic processing the graphene dispersion liquid after mixing the conductive monomers into the graphene dispersion liquid;   step  4  for mixing an initiator into the mixed liquid of the graphene and the conductive monomers such that an in situ polymerization of the conductive monomers is occurred on a surface of the graphene for producing a pre-liquid of a graphene conductive polymer composite material;   step  5  for producing a powder of the graphene conductive polymer composite material by removing solvent and impurity in the pre-liquid of the graphene conductive polymer composite material through a filtration process and a drying process;   step  6  for providing, mixing and stirring a certain proportion of an epoxy resin, a curing agent and an accelerator until the epoxy resin, the curing agent and the accelerator are uniformly distributed such that an epoxy resin glue system is produced;   step  7  for distributing the powder of the graphene conductive polymer composite material into the epoxy resin glue system to produce a pre-material of the graphene polymer conductive film; and   step  8  for deaerating the pre-material of the graphene polymer conductive film to produce the graphene polymer conductive film.   
     
     
         2 . The method of manufacturing the graphene polymer conductive film according to  claim 1 , wherein in the step  1 , an amount of sheet of the powder of the graphene is less than 10, a size of the powder of the graphene is 1˜10 um, a conductivity of the powder of the graphene is greater than 1000 S/m, and the conductive monomers are aniline, pyrrole or thiophene. 
     
     
         3 . The method of manufacturing the graphene polymer conductive film according to  claim 2 , wherein when the conductive monomers in the step  1  are pyrrole, the initiator in the step  4  is ferric chloride, and a molar ratio of the ferric chloride and the pyrrole monomers is 2:1˜1:3. 
     
     
         4 . The method of manufacturing the graphene polymer conductive film according to  claim 2 , wherein when the conductive monomers in the step  1  are aniline or thiophene, the initiator in the step  4  is ammonium persulfate, and a molar ratio of the ammonium persulfate and the aniline or thiophene monomers is 1:1˜4:1. 
     
     
         5 . The method of manufacturing the graphene polymer conductive film according to  claim 1 , wherein in the step  2 , the solvent is one or a mixture of some of water, ethanol, ethylene glycol, acetone, chloroform, N-methylpyrrolidone, tetrahydrofuran, dimethylformamide, or toluene; and a concentration of the graphene dispersion liquid is 0.01 mg/mL˜3 mg/mL. 
     
     
         6 . The method of manufacturing the graphene polymer conductive film according to  claim 1 , wherein in the step  3 , a mass ratio of the graphene and the conductive monomers is 1:30˜10:1 in the mixed liquid of the graphene and the conductive monomers;
 in the step  4 , the in situ polymerization is occurred at −15˜5° C. for 1˜24 hour(s). 
 
     
     
         7 . The method of manufacturing the graphene polymer conductive film according to  claim 1 , wherein in the step  5 , the filtration process is normal filtration or suction filtration, and the impurity in the pre-liquid of the graphene conductive polymer composite material is removed through alternating washing by ethanol and water in the filtration process; the drying process is freeze-drying or is drying at 20˜100° C. 
     
     
         8 . The method of manufacturing the graphene polymer conductive film according to  claim 1 , wherein in the step  6 , the epoxy resin accounts for 80 wt %˜95 wt % of the epoxy resin glue system, the curing agent accounts for 1 wt %˜12 wt % of the epoxy resin glue system, and the accelerator accounts for 0.3 wt %˜5 wt % of the epoxy resin glue system;
 the epoxy resin is bisphenol A type epoxy resin E44, bisphenol A type epoxy resin E51, bisphenol A type epoxy resin E54, bisphenol A type epoxy resin EPON826 or bisphenol A type epoxy resin EPON828; the curing agent is hexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic dihydrazide, adipodihydrazide, dicyandiamide or p-phenylenediamine; the accelerator is 2-ethyl-4-methylimidazole, imidazole, dimethylimidazole or triethylamine. 
 
     
     
         9 . The method of manufacturing the graphene polymer conductive film according to  claim 1 , wherein in the step  7 , a mass ratio of the epoxy resin system and the graphene conductive polymer composite material is 100:2˜30. 
     
     
         10 . A graphene polymer conductive film manufactured by the method of manufacturing the graphene polymer conductive film according to  claim 1 . 
     
     
         11 . A method of manufacturing a graphene polymer conductive film, comprising:
 step  1  for providing a powder of a graphene and a plurality of conductive monomers;   step  2  for providing a solvent and producing a graphene dispersion liquid by stirring and ultrasonic processing the solvent after mixing the powder of the graphene into the solvent;   step  3  for producing a mixed liquid having the graphene and the conductive monomers uniformly distributed by stirring and ultrasonic processing the graphene dispersion liquid after mixing the conductive monomers into the graphene dispersion liquid;   step  4  for mixing an initiator into the mixed liquid of the graphene and the conductive monomers such that an in situ polymerization of the conductive monomers is occurred on a surface of the graphene for producing a pre-liquid of a graphene conductive polymer composite material;   step  5  for producing a powder of the graphene conductive polymer composite material by removing solvent and impurity in the pre-liquid of the graphene conductive polymer composite material through a filtration process and a drying process;   step  6  for providing, mixing and stirring a certain proportion of an epoxy resin, a curing agent and an accelerator until the epoxy resin, the curing agent and the accelerator are uniformly distributed such that an epoxy resin glue system is produced;   step  7  for distributing the powder of the graphene conductive polymer composite material into the epoxy resin glue system to produce a pre-material of the graphene polymer conductive film; and   step  8  for deaerating the pre-material of the graphene polymer conductive film to produce the graphene polymer conductive film;   wherein in the step  1 , an amount of sheet of the powder of the graphene is less than 10, a size of the powder of the graphene is 1˜10 um, a conductivity of the powder of the graphene is greater than 1000 S/m, and the conductive monomers are aniline, pyrrole or thiophene;   wherein when the conductive monomers in the step  1  are pyrrole, the initiator in the step  4  is ferric chloride, and a molar ratio of the ferric chloride and the pyrrole monomers is 2:1˜1:3;   wherein when the conductive monomers in the step  1  are aniline or thiophene, the initiator in the step  4  is ammonium persulfate, and a molar ratio of the ammonium persulfate and the aniline or thiophene monomers is 1:1˜4:1;   wherein in the step  2 , the solvent is one or a mixture of some of water, ethanol, ethylene glycol, acetone, chloroform, N-methylpyrrolidone, tetrahydrofuran, dimethylformamide, or toluene; and a concentration of the graphene dispersion liquid is 0.01 mg/mL˜3 mg/m;   wherein in the step  3 , a mass ratio of the graphene and the conductive monomers is 1:30˜10:1 in the mixed liquid of the graphene and the conductive monomers; in the step  4 , the in situ polymerization is occurred at −15˜5° C. for 1˜24 hour(s);   wherein in the step  5 , the filtration process is normal filtration or suction filtration, and the impurity in the pre-liquid of the graphene conductive polymer composite material is removed through alternating washing by ethanol and water in the filtration process; the drying process is freeze-drying or is drying at 20˜100° C.;   wherein in the step  6 , the epoxy resin accounts for 80 wt %˜95 wt % of the epoxy resin glue system, the curing agent accounts for 1 wt %˜12 wt % of the epoxy resin glue system, and the accelerator accounts for 0.3 wt %˜5 wt % of the epoxy resin glue system; the epoxy resin is bisphenol A type epoxy resin E44, bisphenol A type epoxy resin E51, bisphenol A type epoxy resin E54, bisphenol A type epoxy resin EPON826 or bisphenol A type epoxy resin EPON828; the curing agent is hexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic dihydrazide, adipodihydrazide, dicyandiamide or p-phenylenediamine; the accelerator is 2-ethyl-4-methylimidazole, imidazole, dimethylimidazole or triethylamine;   wherein in the step  7 , the mass ratio of the epoxy resin system and the graphene conductive polymer composite material is 100:2˜30.